JP2016025108A - Wavelength conversion type sealing layer and solar battery module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wavelength conversion type sealing layer for a solar battery that has high durability, is advantageous in cost and can enhance a photoelectric conversion efficiency of a solar battery cell by wavelength-converting light in a wavelength range making no contribution to power generation to light in a wavelength range making contribution to power generation.SOLUTION: A wavelength conversion type sealing material layer has a first region containing at least first organic material and a second region containing at least second organic material. The first organic material is an organic material which absorbs ultraviolet ray and converts to light having a longer wavelength than the absorbed light. The second organic material is an organic material which absorbs light having a longer wavelength than the first organic material and converts to light having a longer wavelength than the absorbed light. The wavelength conversion type sealing material layer is disposed so that incident light passes through the second region before reaching the first region.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a wavelength conversion type sealing material layer particularly suitable for solar cell applications, and a solar cell module using the wavelength conversion type sealing material layer. More specifically, the present invention relates to a solar cell module that can increase power generation efficiency by converting the wavelength of light that does not contribute to power generation into light of a wavelength range that contributes to power generation, and a wavelength conversion type sealing material layer used therefor.

  The use of solar energy provides a promising alternative energy source for conventional fossil fuels, and therefore the development of devices that can convert solar energy into electricity, eg, photovoltaic devices (which also serve as solar cells In recent years, much attention has been paid to the development of such products. Several different types of mature photovoltaic devices have been developed, including silicon-based devices, III-V and II-VI PN junction devices, copper-indium-gallium, to name a few. -Selenium (CIGS) thin film devices, organic sensitizer devices, organic thin film devices, and cadmium sulfide / cadmium telluride (CdS / CdTe) thin film devices. More details regarding these devices can be found in the literature (see, for example, Non-Patent Document 1). However, many photoelectric conversion efficiencies of these devices still have room for improvement, and the development of techniques to improve this efficiency is an ongoing challenge for many researchers.

  In order to improve the conversion efficiency, a solar cell having a wavelength conversion function that converts a wavelength (for example, an ultraviolet region) of incident light that does not contribute to photoelectric conversion into a wavelength that contributes to photoelectric conversion has been studied (for example, , See Patent Document 2). In the above study, a method for forming a light-emitting panel by mixing phosphor powder with a resin raw material has been proposed.

  While wavelength converting inorganic media used in photovoltaic devices and solar cells have been disclosed so far, little work has been reported on the use of photoluminescent organic media in photovoltaic devices to improve efficiency. Not. In contrast to inorganic media, the use of organic media is typically cheaper and easier to use, which makes organic materials a better economic choice. It is attracting attention in that it becomes one of these.

  Further, in the conventional wavelength conversion inorganic medium, the degree of wavelength conversion (the efficiency of wavelength conversion and the shift width of the wavelength before and after the conversion) is not sufficient. In addition, for example, even if a plurality of wavelength conversion media layers are simply combined or a plurality of wavelength conversion media are simply mixed and mixed in a single layer, the wavelength absorption characteristics of the wavelength conversion media itself are different from those of other wavelength conversion media and It has been found that even the wavelength that the solar cell has absorbed and photoelectrically converted is absorbed, and as a result, a negative effect that the photoelectric conversion efficiency hardly improves or decreases can be exhibited.

  In addition, conventionally used inorganic fluorescent materials and organic fluorescent materials are deteriorated by exposure to sunlight, and the wavelength conversion function may be significantly reduced. In addition, it is necessary to absorb and emit light at a wavelength suitable for the characteristics of the solar cell, but it has been difficult to prepare an optimum wavelength.

US Patent Application Publication No. 2009/0151785 Japanese Patent Laid-Open No. 7-142752

  In light of such circumstances, the present invention is highly durable and advantageous in terms of cost, and wavelength conversion of light in a wavelength region that does not contribute to power generation into light in a wavelength region that contributes to power generation is performed. It aims at providing the wavelength conversion type sealing material layer for solar cells which can improve a photoelectric conversion efficiency.

  Moreover, an object of this invention is to provide the solar cell module using the said wavelength conversion type sealing material layer.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the wavelength conversion type sealing material layer shown below and a solar cell module using the same. It came to be completed.

The wavelength conversion type sealing material layer of the present invention is a wavelength conversion type sealing material layer having a first region containing at least a first organic material and a second region containing at least a second organic material,
The first organic substance is an organic substance that absorbs ultraviolet light and converts it into light having a longer wavelength than the absorbed light.
The second organic material is an organic material that absorbs light having a longer wavelength than the first organic material and converts the light into light having a longer wavelength than the absorbed light.
Prior to reaching the first region, the incident light is arranged to pass through the second region.

  By using the wavelength conversion type sealing material layer of the present invention, as light that can contribute to power generation by effectively converting light in a shorter wavelength region to the long wavelength side that has been lost without contributing to power generation so far It can be used more effectively. Further, the wavelength conversion type sealing material layer of the present invention accepts at least one photon having the first wavelength as an input, and at least one photon having a second wavelength longer (larger) than the first wavelength. As an output, a function as a wavelength conversion type sealing material layer is expressed in this process.

  In addition, the present invention has the above-described configuration, so that the light emitted from the first organic substance (organic dye) is further emitted by the second organic substance (organic dye) used for excitation. It is presumed that the light can be converted into visible light having a further distant wavelength than when one kind of organic dye is converted. In particular, due to the organic relationship between the absorption and emission (fluorescence) of the first organic substance and the second organic substance, the degree of wavelength conversion (wavelength conversion efficiency and wavelength before and after conversion) that was not sufficient with conventional wavelength conversion inorganic media ) Can be improved. Moreover, the output of the solar cell can be improved by converting the light into a light of a higher sensitivity region of the power generation layer.

  In particular, even if a layer having a wavelength conversion function is provided, light emission from the wavelength conversion material usually spreads in the same direction, so that light emission is lost not only on the solar cell side but also on the incident light side and the cover glass side. Inevitable. When light is emitted toward the incident light side and the cover glass side, the light does not normally reach the solar battery cell and cannot contribute to the output improvement. However, by using the wavelength conversion type sealing material layer of the present invention, it is possible to reduce the loss of light emission when light is emitted by wavelength conversion, and to contribute to the improvement of the output of the solar battery cell. More specifically, by using the wavelength conversion type sealing material layer of the present invention, the light emitted toward the incident light side and the cover glass side among the light emission of the first organic substance having the absorption wavelength region on the short wavelength side. Is absorbed by the second organic substance located on the outer side (a direction not facing the solar battery cell, for example, a direction away from the solar battery cell), and further emits light, whereby a part thereof is directed again to the solar battery cell. I guess it will be possible.

  Moreover, in the wavelength conversion type sealing material layer of this invention, it is preferable that the 1st organic substance contained in the said 1st area | region is more than the 1st organic substance contained in the said 2nd area | region. The first region may not include the second organic material.

  Moreover, in the wavelength conversion type sealing material layer of this invention, it is preferable that there are more 2nd organic substances contained in the said 2nd area | region than the 1st organic substance contained in the said 1st area | region. Further, the second region may not contain the first organic material.

  By appropriately adjusting the composition and distribution of the first organic substance and / or the second organic substance in each region, a design for improving the desired conversion efficiency according to the cell is facilitated. Note that the term “more” means that the weight of the same compound (such as the same organic compound) is larger.

  Further, in the wavelength conversion type sealing material layer of the present invention, the second organic material is included more between the first region and the second region than the first region, and / or the second region. It can also have a 3rd area | region which contains more said 1st organic substances than an area | region. By having the said structure, the design of the desired conversion efficiency improvement etc. according to a cell may become easy by adjusting suitably the mixing | blending and distribution as the whole wavelength conversion type sealing material layer.

  Moreover, in the wavelength conversion type sealing material layer of this invention, it is preferable to arrange | position so that it may contain more said 1st organic substances in the said 3rd area | region, so that it becomes closer to the said 1st area | region. By having the said structure, it may become possible to contribute to the output improvement of a photovoltaic cell, reducing the loss of the said light emission at the time of making it light-emit by the above-mentioned wavelength conversion more efficiently.

  Moreover, in the wavelength conversion type sealing material layer of this invention, it is preferable to arrange | position so that it may contain more said 2nd organic substances, so that it becomes closer to the said 2nd area | region in the said 3rd area | region. By having the said structure, it may become possible to contribute to the output improvement of a photovoltaic cell, reducing the loss of the said light emission at the time of making it light-emit by the above-mentioned wavelength conversion more efficiently.

  In the wavelength conversion type sealing material layer of the present invention, the first region is a first wavelength conversion type sealing material layer, and the second region is a second wavelength conversion type sealing material layer. It is possible. By having the said structure, it may become possible to contribute to the output improvement of a photovoltaic cell, reducing the loss of the said light emission at the time of making it light-emit by the above-mentioned wavelength conversion more efficiently.

  In addition, the second organic matter is more between the first wavelength conversion type sealing material layer and the second wavelength conversion type sealing material layer of the present invention than the first wavelength conversion type sealing material layer. It can also have a 3rd wavelength conversion type sealing material layer which contains and / or contains the said 1st organic substance more than the said 2nd wavelength conversion type sealing material layer. By having the said structure, the design of the desired conversion efficiency improvement etc. according to a cell may become easy by adjusting suitably the mixing | blending and distribution as the whole wavelength conversion type sealing material layer.

  Further, in the wavelength conversion type sealing material layer of the present invention, the third wavelength conversion type sealing material layer is a plurality of layers, and the layer containing more of the first organic material is the first wavelength conversion type. It is preferable that they are arranged closer to the sealing material layer. By having the said structure, it may become possible to contribute to the output improvement of a photovoltaic cell, reducing the loss of the said light emission at the time of making it light-emit by the above-mentioned wavelength conversion more efficiently.

  Further, in the wavelength conversion type sealing material layer of the present invention, the third long conversion type sealing material layer is a plurality of layers, and the layer containing more of the second organic substance is the second wavelength conversion type. It is preferable that they are arranged closer to the sealing material layer. By having the said structure, it may become possible to contribute to the output improvement of a photovoltaic cell, reducing the loss of the said light emission at the time of making it light-emit by the above-mentioned wavelength conversion more efficiently.

On the other hand, the wavelength conversion-type sealing material layer of the present invention, the relationship of the first organic maximum fluorescence wavelength lambda _1em and the second organic maximum excitation wavelength lambda _2EX and the following formula (Formula (1)) It is characterized by being.
[Formula (1)]
_{λ 1em -80 ≦ λ 2ex ≦ λ} 1em +100 (nm)

  The wavelength conversion type sealing material layer of this invention becomes a wavelength conversion type sealing material layer which has a desirable optical characteristic (high quantum yield etc.) by having the said structure. More specifically, the wavelength conversion type sealing material layer uses the first organic material and the second organic material in the relationship of the above-described formula (1), and thus has not contributed to power generation until now. Therefore, it is possible to effectively convert the light in the shorter wavelength range to the longer wavelength side and effectively use it as light that can contribute to power generation.

  The wavelength of sunlight that is photoelectrically converted by the solar cell is limited to a specific wavelength range. In addition, an ultraviolet absorber is added to most solar cell encapsulants for the purpose of preventing deterioration of the members. On the other hand, in the present invention, ultraviolet rays that could not contribute to power generation can be effectively used by combining organic pigments in a specific relationship. In this case, if the organic dye absorbs even the wavelength region that is originally absorbed by the solar cell and should be photoelectrically converted, the negative effect that the photoelectric conversion efficiency is reduced (negative influence by the combined use) may also occur. It was found that it developed. Therefore, the negative effect is generated by controlling the wavelength band of the second organic substance (organic dye) that absorbs visible light as the above configuration so that the organic dye does not absorb the wavelength range to be photoelectrically converted. I guess that it is possible to prevent.

In addition, the maximum fluorescence wavelength in the present invention refers to a wavelength having a maximum light emission amount among light emitted from the compound (such as an organic compound). In addition, the maximum excitation wavelength in the present invention refers to a wavelength having a maximum amount of light absorption that contributes to fluorescence emission among light absorbed by the compound. More specifically, for example, the maximum fluorescence wavelength λ _1em refers to the wavelength with the maximum amount of light emitted from the light emitted from the first organic material. Further, the maximum excitation wavelength λ _2ex in the present invention refers to a wavelength having a maximum amount of light absorption that contributes to fluorescence emission among light absorbed by the second organic material. Further, the maximum absorption wavelength in the present invention refers to a wavelength at which the amount of light absorbed by the compound is maximum. More specifically, the maximum absorption wavelength λ _1abs in the present invention refers to a wavelength at which the amount of light absorbed by the first organic substance is maximum. The molar extinction coefficient in the present invention means the molar extinction coefficient when irradiated with light having the maximum absorption wavelength of the compound.

In the wavelength conversion type sealing material layer of the present invention, it is preferable that the maximum absorption wavelength λ _1abs of the first organic material is 300 to ₄₀₀ nm. By using the first organic substance, light in the ultraviolet region that is difficult to use (or cannot be used) for photoelectric conversion in a normal solar battery cell can be converted to a longer wavelength side, and the photoelectric conversion efficiency can be further improved. .

Moreover, in the wavelength conversion type sealing material layer of this invention, it is preferable that maximum excitation wavelength (lambda) _2ex of the said 2nd organic substance is 330-500 nm. By using the second organic material, light in the short wavelength region of visible light which is difficult (or cannot be used) for photoelectric conversion in a normal solar battery cell is converted to a longer wavelength side, and the photoelectric conversion efficiency is further improved. It can be easy to improve. In the present invention, the light converted from the first organic substance to the longer wavelength side can also be converted to the longer wavelength side (red shift) to further improve the photoelectric conversion efficiency.

  In the wavelength conversion type sealing material layer of the present invention, the first organic substance is at least one selected from the group consisting of a perylene derivative, a benzoxazole derivative, a benzothiadiazole derivative, a benzotriazole derivative, and a fluorene derivative. Can be included.

  In the wavelength conversion type sealing material layer of the present invention, the second organic substance is at least one selected from the group consisting of a perylene derivative, a benzoxazole derivative, a benzothiadiazole derivative, a benzotriazole derivative, and a fluorene derivative. Can be included.

  Moreover, since the wavelength conversion type sealing material layer of this invention has the above wavelength conversion characteristics, it is preferable to be used especially for a solar cell use. Moreover, it is preferable that the said incident light is sunlight in the wavelength conversion type sealing material layer of this invention.

  On the other hand, the solar cell module of the present invention includes the wavelength conversion type sealing material layer. Since the said solar cell module has the said wavelength conversion type sealing material layer, it becomes a solar cell module which has desirable optical characteristics (high quantum yield etc.).

  Moreover, it is preferable that the solar cell module of this invention is arrange | positioned so that incident light may pass the said wavelength conversion type sealing material layer prior to arrival to a photovoltaic cell. By setting it as the said structure, it becomes possible to more reliably convert the spectrum of the wider range of solar energy into electricity, and can improve photoelectric conversion efficiency effectively.

  In the solar cell module of the present invention, the solar cell is a crystalline silicon solar cell, an amorphous silicon solar cell, a microcrystalline silicon solar cell, a thin film silicon solar cell, a heterojunction solar cell, a multijunction solar cell, a sulfide. It is a cadmium / cadmium telluride solar cell, a CIS thin film solar cell, a CIGS thin film solar cell, a CZTS thin film solar cell, a III-V group solar cell, a dye-sensitized solar cell, or an organic semiconductor solar cell. preferable. The said solar cell module can improve photoelectric conversion efficiency more effectively by using it for the solar cell module which laminates | stacks the said photovoltaic cell. In particular, silicon solar cells have a problem that the photoelectric conversion efficiency is low in the ultraviolet region. In the solar cell module, light can be used more effectively in this wavelength region.

The example of the solar cell module using the wavelength conversion type sealing material layer of this invention is shown. The example of the solar cell module using the wavelength conversion type sealing material layer of this invention is shown. The example of the solar cell module using the wavelength conversion type sealing material layer of this invention is shown. The example of the solar cell module using the wavelength conversion type sealing material layer of this invention is shown. The example of the solar cell module using the wavelength conversion type sealing material layer of this invention is shown. The example of the solar cell module using the wavelength conversion type sealing material layer of this invention is shown. The example of the solar cell module using the wavelength conversion type sealing material layer of this invention is shown.

  Embodiments of the present invention will be described below.

The wavelength conversion type sealing material layer of the present invention is a wavelength conversion type sealing material layer having a first region containing at least a first organic material and a second region containing at least a second organic material,
The first organic substance is an organic substance that absorbs ultraviolet light and converts it into light having a longer wavelength than the absorbed light.
The second organic material is an organic material that absorbs light having a longer wavelength than the first organic material and converts the light into light having a longer wavelength than the absorbed light.
Prior to reaching the first region, the incident light is arranged to pass through the second region.

(Wavelength conversion type sealing material composition)
The wavelength conversion type sealing material layer of this invention can be formed using a wavelength conversion sealing material composition, for example.

  The wavelength conversion sealing material composition absorbs and absorbs ultraviolet light and absorbs light having a wavelength longer than that of the first organic material and the first organic material that converts light having a wavelength longer than the absorbed light. Either or both of the second organic substance and the second organic substance that converts light having a longer wavelength than light are included.

  The first organic substance in the present invention is an organic substance that absorbs ultraviolet rays and converts it into light having a longer wavelength than the absorbed light. In other words, an organic material that can accept at least one photon having a first wavelength as an input and provide at least one photon having a second wavelength longer (larger) than the first wavelength as an output. The organic material may include not only an organic compound but also an organic metal complex or an organic-inorganic hybrid material.

In the present invention, it is preferable that the stalk shift Δλ ₁ of the first organic material is 50 nm or more. By using the first organic material, it is possible to easily convert the wavelength light that does not contribute to power generation to light in the wavelength range that contributes to power generation, and to easily improve the photoelectric conversion efficiency. The Stoke shift in the present invention refers to the difference between the maximum excitation wavelength and the maximum emission wavelength.

In the wavelength conversion type sealing material composition, the first organic substance preferably has a stalk shift Δλ ₁ of 50 nm or more, may be 50 to ₁₀₀ nm, or may be 50 to 70 nm.

In the present invention, the fluorescence quantum yield φ1 of the _first organic material is preferably 85% or more. By using the first organic material, the photoelectric conversion efficiency can be improved more reliably. In addition, the fluorescence quantum yield in the present invention refers to the ratio of the number of photons emitted (or emitted) with respect to the number of absorbed photons when irradiated with light having a maximum excitation wavelength. The emission quantum yield can be measured by measuring the emission quantum yield when excited at the maximum excitation wavelength with MCPD (manufactured by Otsuka Electronics Co., Ltd., software “Ver. 1.10.10.1”). .

In the present invention, the fluorescence quantum yield φ1 of the _first organic material is preferably 85% or more, more preferably 90% or more, and further preferably 93% or more.

In the present invention, the maximum absorption wavelength λ _1abs of the first organic material is preferably ₃₀₀ to 400 nm, ₃₀₀ to 360 nm, or ₃₃₀ to 350 nm.

In the present invention, it is preferable that the first local maximum fluorescence wavelength lambda _1em of organic matter is 350 to 450 nm, may be 380～440Nm, may be 400-420 nm. By using the first organic material, the photoelectric conversion efficiency can be further improved.

  Moreover, an organic fluorescent compound is mention | raise | lifted as said 1st organic substance. As the organic fluorescent compound, known organic dye compounds (organic dyes, organic fluorescent dyes, etc.) can be used. Examples of the organic fluorescent compound include perylene derivatives, pyrene derivatives, benzoxazole derivatives, benzothiazole derivatives, benzothiadiazole derivatives, benzotriazole derivatives, benzimidazole derivatives, benzimidazoline derivatives, benzopyrazole derivatives, indole derivatives, isoindole derivatives, purines Derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, aromatic imide derivatives, benzoxazoyl derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives, bis (triazinylamino) stilbene disulfonic acid derivatives, bisstyryl biphenyl derivatives, bisbenzo Oxazolylthiophene derivatives, pentacene derivatives, fluorescene derivatives, rhodamine derivatives, acridine derivatives, flavones Conductor, fluorene derivatives, cyanine dyes, rhodamine dyes, and, and the like polycyclic aromatic hydrocarbon. Especially, it is preferable that the first organic material includes at least one selected from the group consisting of a perylene derivative, a benzoxazole derivative, a benzothiadiazole derivative, a benzotriazole derivative, and a fluorene derivative.

  As the organic fluorescent compound, more specifically, for example, naphthalimide, perylene, anthraquinone, coumarin, benzocoumarin, xanthene, phenoxazine, benzo [a] phenoxazine, benzo [b] phenoxazine, benzo [C] Phenoxazine, naphthalimide, naphtholactam, azlactone, methine, oxazine, thiazine, diketopyrrolopyrrole, quinacridone, benzoxanthene, thioepindrine, lactamimide, diphenylmaleimide, acetoacetamide, imidazothiazine, benzanthrone, Perylene monoimide, phthalimide, benzotriazole, benzothiadiazole, benzoxazole, pyrimidine, pyrazine, triazole, dibenzofuran, triazine, and derivatives thereof, The Rabbi, and the like Harubitsuru acid derivatives. These compounds may be used alone or in combination of two or more.

  Moreover, an organometallic complex is mention | raise | lifted as said 1st organic substance. As the organometallic complex, a known rare earth metal organic complex or the like can be used. As the organometallic complex, there is no particular limitation on the rare earth element of the central metal element, for example, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, Examples include ytterbium and lutetium. Of these, europium or samarium is preferable. In particular, from the viewpoint of wavelength conversion efficiency, at least one of a europium complex or a samarium complex is preferable.

  Moreover, it does not restrict | limit especially as a ligand which comprises the said organic complex, According to the metal to be used, it can select suitably. Especially, it is preferable that it is a ligand which can form a complex with at least 1 sort (s) of europium or samarium. The ligand is at least one selected from carboxylic acid, nitrogen-containing organic compound, nitrogen-containing aromatic heterocyclic compound, β-diketone, and phosphine oxide, which are neutral ligands. preferable.

  Examples of the carboxylic acid include aliphatic carboxylic acids such as butyric acid, stearic acid, oleic acid, coconut oil fatty acid, t-butylcarboxylic acid, and succinic acid, and aromatic carboxylic acids such as benzoic acid, naphthoic acid, and quinolinecarboxylic acid. Etc.

  Examples of the nitrogen-containing organic compound include aromatic amines such as alkylamines and anilines, nitrogen-containing aromatic heterocyclic compounds, and specifically, 1,10-phenanthroline or bipyridyl. it can. In addition, imidazole, triazole, pyrimidine, pyrazine, aminopyridine, pyridine and derivatives thereof, nucleobases such as adenine, thymine, guanine and cytosine, and derivatives thereof can also be used.

  Examples of β-diketones include 1,3-diphenyl-1,3-propanedione, acetylacetone, benzoylacetone, dibenzoylacetone diisobutyromethane, dibiparoylmethane, 3-methylpentane-2,4dione, 2, 2-dimethylpentane-3,5-dione, 2-methyl-1,3-butanedione, 1,3-butanedione, 3-phenyl-2.4-pentanedione, 1,1,1-trifluoro2,4-pentanedione, 1, 1,1-trifluoro 5,5-dimethyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 3-methyl-2,4-pentanedione, 2-acetylcyclopentanone, 2-acetylcyclohexanone, 1-heptafluoropropyl-3-t-butyl-1,3-propa Dione, 1,3-diphenyl-2-methyl-1,3-propane dione (diphenyl acetylacetone), and 1-Etokishi 1,3-butanedione can be mentioned. Among these, 1,3-diphenyl-1,3-propanedione, acetylacetone, and benzoylacetone are preferable.

  Moreover, it is preferable that it is 0.001-0.5 weight part with respect to 100 weight part of matrix resins of the wavelength conversion type sealing material composition as a compounding quantity of said 1st organic substance, 0.001-0 .3 parts by weight or 0.005 to 0.2 parts by weight may be used.

  The second organic substance in the present invention is an organic substance that absorbs ultraviolet light and converts it into light having a longer wavelength than the absorbed light. In other words, an organic material that can accept at least one photon having a first wavelength as an input and provide at least one photon having a second wavelength longer (larger) than the first wavelength as an output. The organic material may include not only an organic compound but also an organic metal complex or an organic-inorganic hybrid material.

In the present invention, the stalk shift Δλ ₂ of the second organic substance is preferably 50 nm or more, may be 50 to 100 nm, or may be 50 to 70 nm.

In the present invention, the fluorescence quantum yield φ2 of the _second organic substance is preferably 85% or more, more preferably 90% or more, and further preferably 93% or more.

In the present invention, the maximum excitation wavelength λ _2ex of the second organic substance is preferably ₃₃₀ to 500 nm, and may be ₃₄₀ to 450 nm.

In the present invention, the maximum fluorescence wavelength λ _2em of the second organic material is preferably ₄₀₀ to 550 nm, and may be ₄₁₀ to 530 nm. By using the second organic material, the photoelectric conversion efficiency can be further improved.

  Moreover, an organic fluorescent compound is mention | raise | lifted as said 2nd organic substance. As the organic fluorescent compound, known organic dye compounds (organic dyes, organic fluorescent dyes, etc.) can be used. Examples of the organic fluorescent compound include perylene derivatives, pyrene derivatives, benzoxazole derivatives, benzothiazole derivatives, benzothiadiazole derivatives, benzotriazole derivatives, benzimidazole derivatives, benzimidazoline derivatives, benzopyrazole derivatives, indole derivatives, isoindole derivatives, purines Derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, aromatic imide derivatives, benzoxazoyl derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives, bis (triazinylamino) stilbene disulfonic acid derivatives, bisstyryl biphenyl derivatives, bisbenzo Oxazolylthiophene derivatives, pentacene derivatives, fluorescene derivatives, rhodamine derivatives, acridine derivatives, flavones Conductor, fluorene derivatives, cyanine dyes, rhodamine dyes, and, and the like polycyclic aromatic hydrocarbon. Especially, it is preferable that the second organic material includes at least one selected from the group consisting of a perylene derivative, a benzoxazole derivative, a benzothiadiazole derivative, a benzotriazole derivative, and a fluorene derivative.

  As the organic fluorescent compound, more specifically, for example, naphthalimide, perylene, anthraquinone, coumarin, benzocoumarin, xanthene, phenoxazine, benzo [a] phenoxazine, benzo [b] phenoxazine, benzo [C] Phenoxazine, naphthalimide, naphtholactam, azlactone, methine, oxazine, thiazine, diketopyrrolopyrrole, quinacridone, benzoxanthene, thioepindrine, lactamimide, diphenylmaleimide, acetoacetamide, imidazothiazine, benzanthrone, Perylene monoimide, phthalimide, benzotriazole, benzothiadiazole, benzoxazole, pyrimidine, pyrazine, triazole, dibenzofuran, triazine, and derivatives thereof, The Rabbi, and the like Harubitsuru acid derivatives. These compounds may be used alone or in combination of two or more.

  Moreover, an organometallic complex is mention | raise | lifted as said 2nd organic substance. As the organometallic complex, a known rare earth metal organic complex or the like can be used. As the organometallic complex, there is no particular limitation on the rare earth element of the central metal element, for example, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, Examples include ytterbium and lutetium. Of these, europium or samarium is preferable. In particular, from the viewpoint of wavelength conversion efficiency, at least one of a europium complex or a samarium complex is preferable.

  Moreover, it does not restrict | limit especially as a ligand which comprises the said organic complex, According to the metal to be used, it can select suitably. Especially, it is preferable that it is a ligand which can form a complex with at least 1 sort (s) of europium or samarium. The ligand is at least one selected from carboxylic acid, nitrogen-containing organic compound, nitrogen-containing aromatic heterocyclic compound, β-diketone, and phosphine oxide, which are neutral ligands. preferable.

  Examples of the carboxylic acid include aliphatic carboxylic acids such as butyric acid, stearic acid, oleic acid, coconut oil fatty acid, t-butylcarboxylic acid, and succinic acid, and aromatic carboxylic acids such as benzoic acid, naphthoic acid, and quinolinecarboxylic acid. Etc.

  Examples of the nitrogen-containing organic compound include aromatic amines such as alkylamines and anilines, nitrogen-containing aromatic heterocyclic compounds, and specifically, 1,10-phenanthroline or bipyridyl. it can. In addition, imidazole, triazole, pyrimidine, pyrazine, aminopyridine, pyridine and derivatives thereof, nucleobases such as adenine, thymine, guanine and cytosine, and derivatives thereof can also be used.

  Examples of β-diketones include 1,3-diphenyl-1,3-propanedione, acetylacetone, benzoylacetone, dibenzoylacetone diisobutyromethane, dibiparoylmethane, 3-methylpentane-2,4dione, 2, 2-dimethylpentane-3,5-dione, 2-methyl-1,3-butanedione, 1,3-butanedione, 3-phenyl-2.4-pentanedione, 1,1,1-trifluoro2,4-pentanedione, 1, 1,1-trifluoro 5,5-dimethyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 3-methyl-2,4-pentanedione, 2-acetylcyclopentanone, 2-acetylcyclohexanone, 1-heptafluoropropyl-3-t-butyl-1,3-propa Dione, 1,3-diphenyl-2-methyl-1,3-propane dione (diphenyl acetylacetone), and 1-Etokishi 1,3-butanedione can be mentioned. Among these, 1,3-diphenyl-1,3-propanedione, acetylacetone, and benzoylacetone are preferable.

  Moreover, it is preferable that it is 0.0001-0.1 weight part with respect to 100 weight part of matrix resins of the wavelength conversion type sealing material composition as a compounding quantity of said 2nd organic substance, 0.0001-0 0.05 parts by weight, or 0.001 to 0.02 parts by weight.

  The wavelength conversion type sealing material composition has a wavelength conversion function. The said wavelength conversion type sealing material composition converts the wavelength of incident light into a longer wavelength. The wavelength conversion type sealing material composition can be formed by dispersing a first organic substance and / or a second organic substance having a wavelength conversion function in an optically transparent matrix resin.

  In the wavelength conversion type sealing material composition, it is preferable to use an optically transparent matrix resin. Examples of the matrix resin include polyolefins such as polyethylene terephthalate, poly (meth) acrylate, polyvinyl acetate, polyethylene tetrafluoroethylene, polyimide, amorphous polycarbonate, siloxane sol-gel, polyurethane, polystyrene, polyethersulfone, poly Examples include arylate, epoxy resin, and silicone resin. These matrix resins may be used alone or in admixture of two or more.

  Examples of the poly (meth) acrylate include polyacrylate and polymethacrylate, and examples thereof include (meth) acrylic acid ester resins. Examples of the polyolefin resin include polyethylene, polypropylene, and polybutadiene. Examples of the polyvinyl acetate include polyvinyl formal, polyvinyl butyral (PVB resin), and modified PVB.

  As a constituent monomer of the (meth) acrylic ester resin, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate (Meth) acrylic acid alkyl esters such as cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, and benzyl methacrylate. Furthermore, (meth) acrylic acid alkyl ester in which the alkyl group is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like can be given. These compounds may be used alone or in combination of two or more.

  In the (meth) acrylic acid ester, the alkyl group in the ester moiety preferably has 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms.

  As said (meth) acrylic acid ester resin, it is good also as a copolymer using the unsaturated monomer copolymerizable with these besides (meth) acrylic acid ester.

  Examples of the unsaturated monomer include unsaturated organic acids such as methacrylic acid and acrylic acid, styrene, α-methylstyrene, acrylamide, diacetone acrylamide, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, and cyclohexylmaleimide. I can give you. These unsaturated monomers may be used alone or in admixture of two or more.

  Among the above (meth) acrylic acid esters, among them, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, It is preferable to use 2-ethylhexyl methacrylate and its functional group-substituted (meth) acrylic acid alkyl ester. From the viewpoint of durability and versatility, methyl methacrylate and the like can be given as more preferred examples.

  Examples of the copolymer of the (meth) acrylic acid ester and the unsaturated monomer include (meth) acrylic acid ester-styrene copolymer, ethylene-vinyl acetate copolymer, and the like. Of these, ethylene-vinyl acetate copolymer is preferable from the viewpoint of moisture resistance, versatility, and cost, and (meth) acrylic acid ester is preferable from the viewpoint of durability and surface hardness. Further, the combined use of an ethylene-vinyl acetate copolymer and a (meth) acrylic acid ester is preferable from the above viewpoints.

  The ethylene-vinyl acetate copolymer preferably has a vinyl acetate monomer unit content of 10 to 35 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer. More preferably, the above content is preferable from the viewpoint of uniform dispersibility in a matrix resin such as a rare earth complex.

  When the ethylene-vinyl acetate copolymer is used as the optically transparent matrix resin, commercially available products can be used as appropriate. Commercially available products of the ethylene-vinyl acetate copolymer include, for example, Ultrasen (manufactured by Tosoh Corporation), Everflex (manufactured by Mitsui DuPont Polychemical Co., Ltd.), Suntec EVA (manufactured by Asahi Kasei Chemicals Corporation), UBE EVA copolymer ( Ube Maruzen Polyethylene Co., Ltd.), Evertate (Sumitomo Chemical Co., Ltd.), Novatec EVA (Nihon Polyethylene Co., Ltd.), Smitate (Sumitomo Chemical Co., Ltd.), Nipoflex (Tosoh Corp.), and the like.

  In the matrix resin, a crosslinkable monomer may be added to form a resin having a crosslinked structure.

  Examples of the crosslinkable monomer include compounds obtained by reacting α, β-unsaturated carboxylic acid with dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, and polyhydric alcohol ( For example, polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, Trimethylolpropane propoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate (propiol Having 2 to 14 ren groups), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A polyoxyethylene di (meth) acrylate, bisphenol A dioxyethylene di (meth) Acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, etc.), a compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound (for example, tri Methylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc.), polyvalent carboxylic acid (for example, phthalic anhydride), a substance having a hydroxyl group and an ethylenically unsaturated group (for example, β-hydroxy Roxyethyl (meth) acrylate) esterified product, alkyl ester of acrylic acid or methacrylic acid (for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic Acid 2-ethylhexyl ester), urethane (meth) acrylate (for example, reaction product of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylic acid ester, trimethylhexamethylene diisocyanate, cyclohexanedimethanol and 2-hydroxyethyl (meth) A reaction product with an acrylate ester, etc.). These crosslinkable monomers may be used alone or in admixture of two or more. Of these, trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and bisphenol A polyoxyethylene dimethacrylate are preferred as the crosslinkable monomer.

  When the matrix resin containing the crosslinkable monomer is used, for example, a thermal polymerization initiator or a photopolymerization initiator is added to the crosslinkable monomer, and polymerization and crosslinking can be performed by heating or light irradiation to form a crosslinked structure.

  A known peroxide can be appropriately used as the thermal polymerization initiator. Examples of the thermoplastic resin polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, Di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α'-bis (t-butylperoxy) Isopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxybenzate, benzoyl peroxide, etc. be able to. These compounds may be used alone or in combination of two or more.

  For example, 0.1 to 5 parts by weight of the thermal polymerization initiator can be used with respect to 100 parts by weight of the matrix resin.

  As said photoinitiator, the well-known photoinitiator which produces | generates a free radical by an ultraviolet-ray or visible light can be used suitably. Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzoin phenyl ether, benzophenone, N, N′-tetramethyl-4,4′-diamino, and the like. Benzophenones (Michler ketone), benzophenones such as N, N′-tetraethyl-4,4′-diaminobenzophenone, benzyl ketals such as benzyldimethyl ketal (manufactured by Ciba Japan Chemicals, Irgacure 651), benzyl diethyl ketal, 2 , 2-dimethoxy-2-phenylacetophenone, p-tert-butyldichloroacetophenone, acetophenones such as p-dimethylaminoacetophenone, 2,4-dimethylthio Xanthones such as xanthone and 2,4-diisopropylthioxanthone, or hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184), 1- (4-isopropylphenyl) -2-vitoxy-2-methylpropane-1 -On (Ciba Japan Chemicals, Darocur 1116), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck, Darocur 1173) and the like can be mentioned. These may be used singly or in combination of two or more.

  Further, as the photopolymerization initiator, for example, a combination of 2,4,5-triallylimidazole dimer and 2-mercaptobenzoxazole, leucocrystal violet, tris (4-diethylamino-2-methylphenyl) methane, etc. Etc. Further, for example, known additives may be used as appropriate, such as tertiary amines such as triethanolamine for benzophenone.

  The blending amount of the photopolymerization initiator can be 0.1 to 5 parts by weight with respect to 100 parts by weight of the matrix resin, for example.

  The refractive index of the matrix resin is, for example, in the range of 1.4 to 1.7, in the range of 1.45 to 1.65, or in the range of 1.45 to 1.55. In some embodiments, the refractive index of the polymer matrix resin is 1.5.

  The wavelength conversion-type sealing material composition is formed, for example, by dispersing, adsorbing, or impregnating the first organic material having the wavelength conversion function, the second organic material, or both in the matrix resin. can do.

  Further, as a combination of the first organic material and the second organic material, it is preferable that the maximum fluorescence wavelength region of the first organic material overlaps with the maximum excitation wavelength region of the second organic material. In the case of the above combination, ultraviolet light or visible light in the short wavelength region that is difficult (or cannot be used) for photoelectric conversion in a normal solar battery cell is converted to a longer wavelength side to further improve photoelectric conversion efficiency. Can do. Furthermore, the light converted by the first organic material to the longer wavelength side may also be converted to the longer wavelength side to further improve the photoelectric conversion efficiency.

  Moreover, in the said wavelength conversion type sealing material composition, a well-known additive can be suitably contained in the range which does not impair desired performance. Examples of the additive include thermoplastic polymers, antioxidants, UV inhibitors, light stabilizers, organic peroxides, fillers, plasticizers, silane coupling agents, acid acceptors, and clays. These may be used singly or in combination of two or more.

  Moreover, what is necessary is just to carry out according to a well-known method in order to manufacture the said wavelength conversion type sealing material composition. For example, a method of mixing the above materials by a known method using heat kneading, a super mixer (high-speed fluidized mixer), a roll mill, a plast mill, or the like can be given. Moreover, you may perform continuously to manufacture of the said wavelength conversion type sealing material layer.

(Wavelength conversion type sealing material layer)
The wavelength conversion type sealing material layer of the present invention is a wavelength conversion type sealing material layer having a first region containing at least a first organic material and a second region containing at least a second organic material,
The first organic substance is an organic substance that absorbs ultraviolet light and converts it into light having a longer wavelength than the absorbed light.
The second organic material is an organic material that absorbs light having a longer wavelength than the first organic material and converts the light into light having a longer wavelength than the absorbed light.
Prior to reaching the first region, the incident light is arranged to pass through the second region.

  The wavelength conversion type sealing material layer has the first region and the second region. Both the above regions may be continuous or may be interposed with other regions. Each region includes, for example, the abundance (weight, mole, fluorescence quantum yield, etc.) of each or both of the first organic material and the second organic material in each region, and the first organic material and the second organic material. It can be distinguished and identified by the abundance ratio with the organic matter.

  In the wavelength conversion type sealing material layer, the first region includes at least a first organic substance. The first region may further include the second organic material. It is preferable that the first organic material included in the first region is larger than the first organic material included in the second region. The first region may not include the second organic material.

  In addition, the abundance ratio of the first organic substance and the second organic substance in the first region can be, for example, 100: 0 based on the weight, and may be 95:90. It may be 10, 80:20, 70:30, 60:40, or 50:50. In addition, it is sufficient that the ratio of the first organic substance in the first region is higher than that in the second region. For example, the ratio in the first region is 30:70 or 20:80. One organic substance may be less than the second organic substance.

  In the wavelength conversion type sealing material layer, the second region includes at least a second organic substance. The second region may further contain the first organic material. The second organic material contained in the second region is preferably more than the first organic material contained in the first region. Further, the second region may not contain the first organic material.

  In addition, the abundance ratio of the first organic substance and the second organic substance in the second region can be, for example, 100: 0 based on the weight, and may be 95:90. It may be 10, 80:20, 70:30, 60:40, or 50:50. Further, it is sufficient that the ratio of the second organic substance existing in the second region is higher than that in the first region. For example, the ratio in the second region is 30:70 or 20:80. Two organic substances may be less than the first organic substance.

  Further, in the wavelength conversion type sealing material layer, the second organic material is contained more between the first region and the second region than the first region, and / or from the second region. Can also have a third region containing more of the first organic material. The third region may have a difference in the abundance ratio between the first organic substance and the second organic substance in the region continuously or stepwise. Further, another region may be interposed in the third region. Further, another region may be interposed between the third region and the first region or the second region. Further, when there is a difference in the abundance ratio as described above in the third region, it is preferable that the third region is disposed so as to contain more of the first organic substance as it is closer to the first region. In addition, when there is a difference in the abundance ratio as described above in the third region, it is preferable that the third region is arranged so as to contain more of the second organic matter as it is closer to the second region. For example, when the incident light passes through the wavelength conversion type sealing material layer, the wavelength conversion type sealing is performed such that the incident light increases in the first organic substance continuously, gradually, or stepwise. It is preferable that the first organic material is disposed and present in the material layer. In addition, for example, when the incident light passes through the wavelength conversion type sealing material layer, the wavelength conversion type is such that the incident light becomes less in the second organic material continuously, gradually, or stepwise. It is preferable that the first organic material is disposed and present in the sealing material layer.

  In the wavelength conversion type sealing material layer, the first region is a first wavelength conversion type sealing material layer, and the second region is a second wavelength conversion type sealing material layer. Is possible. The two layers may be continuous, and other layers may be interposed as long as the effects of the present invention are not impaired.

  In addition, between the first wavelength conversion type sealing material layer and the second wavelength conversion type sealing material layer, more of the second organic substance than the first wavelength conversion type sealing material layer, and Alternatively, it may be possible to have a third wavelength conversion type sealing material layer containing more of the first organic material than the second wavelength conversion type sealing material layer. Further, the third wavelength conversion type sealing material layer has a layer in which the abundance ratio of the first organic substance and the second organic substance is the same or different in a continuous or stepwise manner. Also good. Further, another wavelength conversion type sealing material layer is interposed between the third wavelength conversion type sealing material layer and the first wavelength conversion type sealing material layer or the second wavelength conversion type sealing material layer. Also good. Moreover, when the said 3rd wavelength conversion type sealing material layer is a several layer, the wavelength conversion type sealing material layer which contains more said 1st organic substances, so that it becomes closer to the said 1st wavelength conversion type sealing material layer It is preferable that they are arranged in a line. Further, when there is a difference in the abundance ratio as described above in the third wavelength conversion type sealing material layer, the closer to the second wavelength conversion type sealing material layer, the more the layer containing the second organic matter. It is preferable to arrange them side by side. For example, when the incident light passes through the wavelength conversion type sealing material layer, the wavelength conversion type sealing is performed such that the incident light increases in the first organic substance continuously, gradually, or stepwise. It is preferable that the third wavelength conversion type sealing material layer is disposed and present in the material layer. In addition, for example, when the incident light passes through the wavelength conversion type sealing material layer, the wavelength conversion type is such that the incident light becomes less in the second organic material continuously, gradually, or stepwise. It is preferable that the third wavelength conversion type sealing material layer is disposed and present in the sealing material layer.

  About the wavelength conversion type sealing material layer of this invention, although a simple schematic diagram is shown in FIGS. 1-7 as an example, this invention is not limited to these. 1 to 7 are illustrations of the solar cell module 1. In FIG. 1, the wavelength conversion type sealing material layer 20 is provided in the photovoltaic cell 30, The surface protective layer 10 is provided in the other side. In this case, normally, the incident light enters from the surface protective layer 10 side and reaches the solar battery cell 30 via the wavelength conversion type sealing material layer 20. In the layer of the wavelength conversion type sealing material layer 20, there are a first region 61 and a second region 62. Incident light in a wavelength region that is not absorbed in the first region passes through the surface protective layer 10, the second region 62, and the first region 61 in order, and reaches the solar battery cell 30. On the other hand, incident light in the wavelength region that is absorbed by the first organic material in the first region passes through the surface protective layer 10 and the second region 62 in order, and is absorbed by the organic material in the first region 61. A part of the light emitted from the first organic material reaches the solar battery cell 30 as it is. Further, another part of the light emitted from the first organic material is absorbed by the second organic material in the second region toward the second region side. A part of the light emitted from the second organic material reaches the solar battery cell 30 as it is.

  FIG. 2 is an example having a first region 61, a second region 62, and a third region 63 in the layer of the wavelength conversion type sealing material layer 20. The third region 63 is between the first region 61 and the second region 62. 3-5 is an example in case each said area | region is a layer. For example, in FIG. 3, the first wavelength conversion type sealing material layer 21 and the second wavelength conversion type sealing material layer 22 are combined to form the wavelength conversion type sealing material layer 20. Similarly, in FIG. 5, the first wavelength conversion type sealing material layer 21, the second wavelength conversion type sealing material layer 22, and the third wavelength conversion type sealing material layer 23 are combined to form a wavelength conversion type sealing material layer. 20 is formed. 6 and 7 are examples in which the area display in the case of FIG. 1 is omitted. Moreover, in any case, as shown in FIGS. 4 and 7, a sealing material layer 40 and a back sheet 50 can be appropriately provided on the surface protective layer 10 and the back side of the solar battery cell. Moreover, as long as the said function of the said solar cell sealing material layer is not impaired between these each layers, you may interpose other layers, such as an adhesive material layer and an adhesive layer, suitably. Moreover, you may use the wavelength conversion type sealing material layer of this invention suitably as said sealing material layer for back surfaces.

  The wavelength conversion type sealing material layer of this invention can be formed using the said wavelength conversion type sealing material composition, for example.

  What is necessary is just to carry out according to a well-known method in order to manufacture the said wavelength conversion type sealing material layer. For example, a composition obtained by mixing each of the above materials by a known method using heat kneading, a super mixer (high-speed fluid mixing machine), a roll mill, a plast mill, etc., is subjected to ordinary extrusion molding, calendar molding (calendering), vacuum heat It can be suitably produced by a method of forming a sheet-like material by molding under pressure or the like. Moreover, after forming the said layer on PET film etc., it can manufacture by the method of transcribe | transferring to a surface protective layer. Further, a method of simultaneously kneading and melting and applying with a hot melt applicator can be used.

  More specifically, for example, the wavelength conversion-type sealing material composition containing the matrix resin, the first organic material, and / or the second organic material is directly applied to a surface protective layer or a separator. Alternatively, the above material may be applied as a mixed composition with other materials. Moreover, you may form the said wavelength conversion type sealing material composition by vapor deposition, sputtering, the aerosol deposition method, etc.

  When applied as the mixed composition, the matrix resin preferably has a melting point of 50 to 250 ° C., more preferably 50 to 200 ° C., and 50 to 180 ° C. in consideration of processability. More preferably. For example, when the melting point of the wavelength conversion type sealing material composition is 50 to 250 ° C., the kneading and melting and application temperature of the composition are preferably performed at a temperature obtained by adding 30 to 100 ° C. to the melting point.

  Also, in some embodiments, the wavelength converting encapsulant layer is manufactured into a thin film structure by the following steps: (i) The polymer (matrix resin) powder is a solvent (eg, tetrachloroethylene (TCE) in a predetermined ratio. ), Preparing a polymer solution dissolved in cyclopentanone, dioxane, etc.) (ii) mixing a luminescent dye (fluorescent dye compound) containing the polymer mixture with the luminescent dye in a predetermined weight ratio Preparing a dye-containing polymer solution, (iii) pouring the dye / polymer thin film directly onto the glass substrate, after which the substrate is allowed to run from room temperature up to 100 ° C. in 2 hours Forming by removing the residual solvent by further vacuum heating overnight at 130 ° C. And (iv) peeling the dye / polymer thin film in water before use, and then completely drying the free-standing polymer film; (v) the thickness of the film, the concentration of the dye / polymer solution and the evaporation It can be controlled by changing the speed.

  In addition, when processing by performing the above heat-kneading treatment or the like, if the melting point of the fluorescent dye compound is excessively high, it becomes difficult to uniformly disperse and dissolve in the system (in the polymer matrix, etc.). The dye may be difficult to uniformly disperse. Therefore, it is preferable that the fluorescent dye compound has a melting point of 250 ° C. or lower, desirably 220 ° C. or lower, and more desirably 210 ° C. or lower. However, inconveniences such as bleed out may occur even when the temperature is too low, and those having a melting point of 50 ° C. or lower may be inferior in the above process. Therefore, the melting point is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher. By using the chromophore of the present invention as described above, it becomes easy to obtain uniformity, particularly when it is made into a sheet, and it is particularly excellent in production and workability.

  Moreover, in the said manufacture, after each wavelength conversion type sealing material layer is produced separately, it may bond and laminate | stack, and each layer may be produced simultaneously by extrusion molding etc.

  In addition, the thickness of the wavelength conversion type sealing material layer (the thickness of the whole wavelength conversion type sealing material layer when plural layers are laminated) is preferably 20 to 2000 μm, for example, and may be 50 to 1000 μm. 200 to 800 μm may be used. If the thickness is less than 20 μm, the wavelength conversion function is hardly exhibited. On the other hand, when it becomes thicker than 2000 micrometers, adhesiveness with another layer falls and it is disadvantageous also in cost.

  Moreover, the thickness of each wavelength conversion type sealing material layer in the case of laminating a plurality of the wavelength conversion type sealing material layers is, for example, preferably 10 to 1500 μm, and may be 30 to 1000 μm. It may be 700 μm. If the thickness is thinner than 10 μm, the wavelength conversion function of the layer is hardly exhibited. On the other hand, when it becomes thicker than 1500 micrometers, adhesiveness with another layer falls and it is disadvantageous also in cost.

  The optical thickness (absorbance) of the wavelength conversion type sealing material layer (in the case of stacking a plurality of layers, the optical thickness of the whole wavelength conversion type sealing material layer) is preferably from 0.5 to 6, and preferably from 1 to 4 Is more preferable, and it is further more preferable that it is 1-3. If the absorbance is low, the wavelength conversion function is hardly exhibited. On the other hand, if the absorbance is too large, it is disadvantageous in terms of cost. The absorbance is a value calculated according to Lambert-Beer law.

  In addition, the optical thickness of each wavelength conversion type sealing material layer in the case where a plurality of the wavelength conversion type sealing material layers are laminated is, for example, preferably 0.001 to 5, and 0.01 to 4. It may be 0.04-3. When the said light absorbency is low, the wavelength conversion function of the said layer will become difficult to express. On the other hand, if the absorbance is too large, it is disadvantageous in terms of cost.

Further, in the wavelength conversion type sealing material layer, the relationship of the first organic maximum fluorescence wavelength lambda _1em and the maximum excitation wavelength lambda _2EX and the following formula of a second organic (formula (1)), that is, preferably in the _{λ 1em -80 ≦ λ 2ex ≦ λ} 1em +100 (nm), may be a _{λ 1em -70 ≦ λ 2ex ≦ λ} 1em +90 (nm), λ 1em -65 ≦ λ 2ex ≦ λ 1em It may be +80 (nm). The wavelength conversion type sealing material layer uses the first organic material and the second organic material in the relationship of the following formula (1). It can be used more effectively as light that can effectively convert light to the longer wavelength side and contribute to power generation.
[Formula (1)]
_{λ 1em -80 ≦ λ 2ex ≦ λ} 1em +100 (nm)

In the wavelength conversion type sealing material layer, the _relationship between the maximum absorption wavelength λ _1abs of the first organic substance and the maximum excitation wavelength λ _2ex of the second organic substance is _expressed by the following formula (formula (2)), that is, λ It is preferable that _2ex− λ _1abs ≧ 5 (nm). The relationship of the following formula (formula (2)) may be λ _2ex −λ _1abs ≧ 10 (nm), λ _2ex −λ _1abs ≧ 50 (nm), or λ _2ex −λ _1abs ≧ It may be 60 (nm), λ _2ex −λ _1abs ≧ 70 (nm), or λ _2ex −λ _1abs ≧ 80 (nm). The wavelength conversion type sealing material layer has a configuration satisfying the above relationship, so that the second organic material effectively converts the light emitted from the first organic material into a longer wavelength region and fluorescently emitted. It becomes easy to use for excitation, and then the second organic substance shifts to a longer wavelength region (red shift) and causes fluorescence emission, so that light in a wavelength region that does not contribute to power generation becomes light in a wavelength region that contributes to power generation. It is estimated that the wavelength can be converted.
[Formula (2)]
λ _2ex −λ _1abs ≧ 5 (nm)

Also, as with the wavelength conversion type sealing material composition layer, in the wavelength conversion type sealing material composition, the maximum excitation wavelength lambda _2EX maximum fluorescence wavelength lambda _1em and the second organic material in the first organic Is preferably the relationship of the above formula (formula (1)), and is preferably the relationship of the above formula (formula (2)).

Further, in the wavelength conversion type sealing material layer, the first organic substance is expressed by a product of the reciprocal number of the weight part P ₁ , the molar extinction coefficient ε ₁ , and the molecular weight Mw _{1 in} the wavelength conversion type sealing material layer. The index C ₁ to be
The ratio of the second organic material to the index C ₂ represented by the product of the reciprocal of the weight part P ₂ , molar extinction coefficient ε ₂ , and molecular weight Mw _{2 in} the wavelength conversion type sealing material layer (formula (3 )) Is preferably 0.001 ≦ C ₂ / C ₁ ≦ 0.5, and may be 0.002 ≦ C ₂ / C ₁ ≦ 0.5, or 0.003 ≦ C ₂ / C. _It may be ₁ ≦ 0.48, or 0.004 ≦ C ₂ / C ₁ ≦ 0.48.
[Formula (3)]
C ₂ / C ₁ = [(P ₂ × ε ₂ ) / Mw ₂ ] / [(P ₁ × ε ₁ ) / Mw ₁ ]

  Moreover, after satisfy | filling so that the ratio of said Formula (3) may become a specific range as a combination compounding quantity of a said 1st organic substance and a said 2nd organic substance, the matrix resin of a wavelength conversion type sealing material layer The blending amounts of the first organic substance and the second organic substance are preferably 0.001 to 0.5 parts by weight and 0.0001 to 0.1 parts by weight with respect to 100 parts by weight. It may be 001 to 0.3 parts by weight and 0.0001 to 0.05 parts by weight, or 0.005 to 0.2 parts by weight and 0.001 to 0.02 parts by weight.

  In the wavelength conversion type sealing material layer, the abundances and content ratios of the first organic substance and the second organic substance used are in any stage of the wavelength conversion type sealing material layer and the solar cell module. Even so, it can be estimated or confirmed by detecting and analyzing secondary ions. For example, the fluorescent dye compound can be analyzed and evaluated by detecting a negative secondary ion at a peak derived from a heterocyclic structure (for example, a benzothiadiazole skeleton or a benzotriazole skeleton).

(Solar cell module)
The solar cell module 1 of the present invention includes the wavelength conversion sealing material layer 20 and the solar cells 30. As an example, FIGS. 1 to 7 show simple schematic diagrams, but the present invention is not limited to these. Moreover, the sealing material layer 40 and the back sheet | seat 50 can also be suitably provided in the back surface side of the surface protective layer 10 and a photovoltaic cell. Moreover, as long as the said function of the said solar cell sealing material layer is not impaired between these each layers, you may interpose other layers, such as an adhesive material layer and an adhesive layer, suitably. Moreover, you may use the wavelength conversion type sealing material layer of this invention suitably as said sealing material layer for back surfaces.

  Since the said solar cell module is provided with the said wavelength conversion type sealing material layer, it can convert into the wavelength which can contribute to photoelectric conversion normally the wavelength which does not contribute to photoelectric conversion. Specifically, a certain wavelength can be converted into a longer wavelength, for example, a wavelength shorter than 370 nm can be converted into a wavelength of 370 nm or more. In particular, the wavelength in the ultraviolet region (10 nm to 365 nm) is converted to the wavelength in the visible light region (370 to 800 nm). Moreover, the range of the wavelength which contributes to photoelectric conversion changes with the kind of solar cell, for example, even if it is a silicon-type solar cell, it changes with the crystal | crystallization forms of the silicon used. For example, in the case of an amorphous silicon solar cell, it is considered to be about 400 nm to 700 nm, and in the case of a polycrystalline silicon solar cell, about 600 nm to 1100 nm. For this reason, the wavelength contributing to photoelectric conversion is not necessarily limited to the wavelength in the visible light region.

  Examples of the solar battery cell include a crystalline silicon solar battery, an amorphous silicon solar battery, a microcrystalline silicon solar battery, a thin film silicon solar battery, a heterojunction solar battery, a multijunction solar battery, a cadmium sulfide / cadmium telluride solar battery, A CIS thin film solar cell, a CIGS thin film solar cell, a CZTS thin film solar cell, a III-V group solar cell, a dye-sensitized solar cell, or an organic semiconductor solar cell can be used. The solar battery cell is preferably a crystalline silicon solar battery.

  In the production of the solar cell module, the solar cell encapsulant layer may be transferred to the solar cell or the like, or may be directly coated on the solar cell. Moreover, you may form the said sealing material layer for solar cells, and another layer simultaneously.

  Moreover, it is preferable that the solar cell module of this invention is arrange | positioned so that incident light may pass the said wavelength conversion type sealing material layer prior to arrival to a photovoltaic cell. By setting it as the said structure, it becomes possible to more reliably convert the spectrum of the wider range of solar energy into electricity, and can improve photoelectric conversion efficiency effectively.

  As the surface protective layer, a known layer used as a surface protective layer for solar cells can be used. Examples of the surface protective layer include a front sheet and glass. As said glass, various things, such as a white board and the presence or absence of embossing, can be used suitably, for example.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below.

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極大吸収波長：３４５ｎｍ
極大励起波長：３４５ｎｍ
極大蛍光波長：４１５ｎｍ
分子量：４３９．６４
［化合物Ｂ］

４，７−ビス（４−イソブチルオキシフェニル）−２、１，３−ベンゾチアジアゾール
極大吸収波長：４２０ｎｍ
極大励起波長：４３０ｎｍ
極大蛍光波長：５２０ｎｍ
分子量：４３２．５８
［化合物Ｃ］

４，７−ジフェニル−２−イソブチル−２Ｈ−ベンゾトリアゾール
極大吸収波長：３４０ｎｍ
極大励起波長：３３０ｎｍ
極大蛍光波長：４００ｎｍ
分子量：３２７．４２
［化合物Ｄ］

４，７−ビス（ジフェニルアミノフェニル）−２Ｈ−２−ピリミジニル−２−ベンゾトリアゾール
極大吸収波長：４５０ｎｍ
極大励起波長：４７０ｎｍ
極大蛍光波長：５４０ｎｍ
分子量：６８３．８
［化合物Ｅ］

ビス（ｔ−ブチルベンゾオキサゾリル）チオフェン
極大吸収波長：３７５ｎｍ
極大励起波長：３４０−３９０ｎｍ
極大蛍光波長：４３０ｎｍ
分子量：４３０．５６
［化合物Ｆ］

４，７−ビス（４−イソブチルオキシフェニル）−２−イソブチル−２Ｈ−ベンゾトリアゾール
極大吸収波長：３６０ｎｍ
極大励起波長：３５０ｎｍ
極大蛍光波長：４３５ｎｍ
分子量：４７１．６３
［化合物Ｇ］

４，７−ビス（４−ｔ−ブチルフェニル）−２、１，３−ベンゾチアジアゾール
極大吸収波長：３９５ｎｍ
極大励起波長：４００ｎｍ
極大蛍光波長：４９０ｎｍ
分子量：４００．５８ (organic matter)
In the examples and comparative examples, the following fluorescent compounds were used.
[Compound A]

4,7-bis (4-t-butylphenyl) -2-isobutyl-2H-benzotriazole Maximum absorption wavelength: 345 nm
Maximum excitation wavelength: 345 nm
Maximum fluorescence wavelength: 415 nm
Molecular weight: 439.64
[Compound B]

4,7-bis (4-isobutyloxyphenyl) -2,1,3-benzothiadiazole Maximum absorption wavelength: 420 nm
Maximum excitation wavelength: 430 nm
Maximum fluorescence wavelength: 520 nm
Molecular weight: 432.58
[Compound C]

4,7-diphenyl-2-isobutyl-2H-benzotriazole Maximum absorption wavelength: 340 nm
Maximum excitation wavelength: 330 nm
Maximum fluorescence wavelength: 400nm
Molecular weight: 327.42
[Compound D]

4,7-bis (diphenylaminophenyl) -2H-2-pyrimidinyl-2-benzotriazole Maximum absorption wavelength: 450 nm
Maximum excitation wavelength: 470 nm
Maximum fluorescence wavelength: 540 nm
Molecular weight: 683.8
[Compound E]

Bis (t-butylbenzoxazolyl) thiophene Maximum absorption wavelength: 375 nm
Maximum excitation wavelength: 340-390 nm
Maximum fluorescence wavelength: 430 nm
Molecular weight: 430.56
[Compound F]

4,7-bis (4-isobutyloxyphenyl) -2-isobutyl-2H-benzotriazole Maximum absorption wavelength: 360 nm
Maximum excitation wavelength: 350 nm
Maximum fluorescence wavelength: 435 nm
Molecular weight: 471.63
[Compound G]

4,7-bis (4-t-butylphenyl) -2,1,3-benzothiadiazole Maximum absorption wavelength: 395 nm
Maximum excitation wavelength: 400 nm
Maximum fluorescence wavelength: 490 nm
Molecular weight: 400.58

(Other compounds)
Matrix resin: Summitate KA30, ethylene vinyl acetate (EVA) resin (Sumitomo Chemical Co., Ltd.)
Peroxide: Perbutyl E, t-butyl peroxy-2-ethylhexyl monocarbonate (manufactured by NOF Corporation)
Crosslinking aid: TAIC, triallyl isocyanurate (Nippon Kasei Co., Ltd.)
Antioxidant: BHT, dibutylhydroxytoluene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Light stabilizer: Tinuvin 144, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalo Nate (BASF)
Silane coupling agent: KBM503, 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone).

(Encapsulant)
In each Example / Comparative Example, each sealing material layer (sealing sheet) was produced by the following method based on the formulation of each compound.

[Example 1, Comparative Example 1]
[Multi-layer encapsulating sheet]
A film having a thickness of 300 μm was prepared using a resin in which different types of wavelength conversion agents were blended in a single composition so as to have a predetermined concentration. These two different films were bonded together to produce a film having a thickness of 600 μm. This film was sandwiched between two pieces of white sheet glass and bonded under the condition of 80 ° C. to produce a multilayered sealing sheet. In addition, phr in the table means the number of added parts of each component with respect to 100 parts by weight of the resin.

[Comparative Example 6]
[Single-layer encapsulating sheet]
A film having a thickness of 600 μm was prepared using a resin in which two kinds of wavelength conversion agents used in a multi-layered sealing sheet were mixed and blended to have a predetermined concentration. This film was sandwiched between two pieces of white sheet glass and bonded under the condition of 80 ° C. to produce a single-structure sealing sheet. In addition, phr in the table means the number of added parts of each component with respect to 100 parts by weight of the resin.

[Examples 2-5, Comparative Examples 2-5, 7, 8]
[Multi-layer encapsulating sheet]
A film having a thickness of 300 μm was prepared using a resin in which different types of wavelength conversion agents were blended in a single composition so as to have a predetermined concentration. These two different films were laminated to produce a multilayer film. This film was sandwiched between two pieces of white sheet glass and bonded under the condition of 80 ° C. to produce a multilayered sealing sheet. In addition, phr in the table means the number of added parts of each component with respect to 100 parts by weight of the resin.

(Measurement of maximum absorption wavelength)
The maximum absorption wavelength was measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, V-560, wavelength range of 300 to 800 nm). The wavelength showing the maximum absorbance in the absorption spectrum was defined as the maximum absorption wavelength.

(Maximum excitation wavelength / maximum emission wavelength)
The maximum excitation wavelength and the maximum emission wavelength are measured using a fluorescence spectrophotometer (F-4500, manufactured by Hitachi High-Technologies Corporation), and the emission wavelength that maximizes the emission intensity in the (excitation-emission) three-dimensional measurement is maximized. Among the excitation spectra of the emission wavelength and the maximum emission wavelength, the wavelength showing the maximum value of the emission intensity was defined as the maximum excitation wavelength.

(Solar cell module creation)
The sealing sheet obtained above is cut into 20 cm × 20 cm, tempered glass (manufactured by Asahi Glass Co .: Solite) as a protective glass, sealing sheet, solar cell (manufactured by Q Cell: Q6LTT3-G2-200 / 1700 -A, crystalline silicon type), backside sealing sheet (400 μm thick EVA sheet), PET film as a back sheet, 140 using a vacuum laminator (NPC Corporation: LM-50x50-S) Lamination was performed under the conditions of ° C., vacuum for 5 minutes, and pressure for 10 minutes to produce a solar cell module.

(Reflectance measurement)
Using the obtained sample, an integrating sphere was attached to a spectrophotometer (manufactured by JASCO Corporation, V-660), and the reflectance was measured. From the obtained spectrum information, the amount of reflected light from the sheet under each condition was evaluated.

(Spectral sensitivity measurement)
Using the solar cell module, measurement was performed using a spectral sensitivity measuring device (CEP-25RR, manufactured by Spectrometer Co., Ltd.), and external quantum efficiency measurement was performed. From the obtained spectrum information, the external quantum efficiency of the solar battery cell under each condition was evaluated.

(Jsc measurement)
The spectral sensitivity of the solar cell module was measured using a spectral sensitivity measuring device (CEP-25RR, manufactured by Spectrometer Co., Ltd.), and a Jsc value calculated from the spectral sensitivity measurement was obtained. The Jsc value refers to a short-circuit current density calculated by calculating a spectral sensitivity spectrum obtained from sample measurement by a spectral sensitivity measuring device and reference sunlight.

  The measurement result when using each obtained sealing material layer (sealing sheet) to the following Tables 3-7 is shown. In addition, Example 1 and Comparative Example 1 are multi-layered encapsulating material layers, Example 1 arranges the layer of Compound B on the light source side (incident light side), and Comparative Example 1 shows the compound A The layer is disposed on the light source side (incident light side). Moreover, the comparative example 6 is a sealing material layer of a single layer structure. Further, the output is calculated by calculating the increase / decrease ratio (Jsc improvement rate) of the Jsc value in each example / comparative example with respect to the Jsc value when only EVA resin is used.

  As a result of the measurement, as shown in Tables 3 to 7, for example, in Example 1 (2 to 1), the same sealing material is used, and the reflectance is higher than that in Comparative Example 1 (1 to 2) in which the stacking order is opposite. Became lower. From this, it is presumed that the compound B absorbs the light emission of the compound A in the sealing material A toward the light source side and converts it into light emission toward the outside of the integrating sphere. That is, in Example 1, it turned out that the reflected light quantity from a sealing material has been reduced.

  Moreover, as shown in Tables 3 to 7, for example, in Example 1 (2 to 1), the same sealing material is used, and the solar cell is compared with Comparative Example 1 (1 to 2) in which the stacking order is opposite. The short circuit current value became high. From this, it is estimated that more light can be irradiated to the solar cell by the above mechanism by using the wavelength conversion type sealing material layer of the present invention. Furthermore, compared with the single-layer sealing material (Comparative Example 2) produced by mixing the same composition, 0.4% improvement in the short-circuit current value was observed, and the solar cells were irradiated with light more efficiently. I understood that it was made.

DESCRIPTION OF SYMBOLS 1 Solar cell module 10 Surface protective layer 20 Wavelength conversion type sealing material layer 21 1st wavelength conversion type sealing material layer 22 2nd wavelength conversion type sealing material layer 23 3rd wavelength conversion type sealing material layer 30 Solar cell 40 Back surface sealing material layer 50 Back sheet 61 1st area | region 62 2nd area | region 63 3rd area | region

Claims (20)

A wavelength conversion type encapsulant layer having a first region containing at least a first organic substance and a second region containing at least a second organic substance,
The first organic material is an organic material that absorbs ultraviolet light and converts it into light having a longer wavelength than the absorbed light.
The second organic material is an organic material that absorbs light having a longer wavelength than the first organic material and converts the light into light having a longer wavelength than the absorbed light.
Incident light is arranged to pass through the second region prior to reaching the first region;
Wavelength conversion type sealing material layer.   2. The wavelength conversion type sealing material layer according to claim 1, wherein the first organic material included in the first region is larger than the first organic material included in the second region.   3. The wavelength conversion type sealing material layer according to claim 1, wherein the second organic material contained in the second region is larger than the second organic material contained in the first region.   The wavelength conversion type sealing material layer according to claim 1, wherein the first region does not contain the second organic substance.   The wavelength conversion type sealing material layer in any one of Claims 1-4 with which the said 2nd area | region does not contain a said 1st organic substance.   A third region between the first region and the second region, including more of the second organic material than the first region and / or including more of the first organic material than the second region. The wavelength conversion type sealing material layer in any one of Claims 1-5 which has these.   The wavelength conversion type sealing material layer according to claim 6, wherein in the third region, the wavelength conversion type sealing material layer is disposed so as to contain more of the first organic substance as being closer to the first region.   8. The wavelength conversion type sealing material layer according to claim 6, wherein in the third region, the wavelength conversion type sealing material layer is disposed so as to contain more of the second organic material as being closer to the second region.   The wavelength conversion type sealing according to any one of claims 1 to 5, wherein the first region is a first wavelength conversion type sealing material layer, and the second region is a second wavelength conversion type sealing material layer. Material layer.   Between the wavelength-converting encapsulant layer and the wavelength-converting encapsulant layer, the second organic material is included more than the first wavelength-converting encapsulant layer, and / or the second The wavelength conversion type sealing material layer of Claim 9 which has a 3rd wavelength conversion type sealing material layer containing more said 1st organic substances than a wavelength conversion type sealing material layer.   The third wavelength conversion type encapsulant layer is a plurality of layers, and the layer containing more of the first organic material is disposed closer to the first wavelength conversion type encapsulant layer. Item 11. The wavelength conversion type sealing material layer according to Item 10.   The third long conversion type sealing material layer is a plurality of layers, and the layer containing more of the second organic substance is disposed so as to be closer to the second wavelength conversion type sealing material layer. Item 12. The wavelength conversion type sealing material layer according to Item 10 or 11. The wavelength conversion type sealing material layer in any one of Claims 1-12 whose maximum absorption wavelength (lambda) _1abs of said 1st organic substance is 300-400 nm. The wavelength conversion type sealing material layer in any one of Claims 1-13 whose maximum excitation wavelength (lambda) _2ex of a said 2nd organic substance is 330-500 nm. Said first maximum fluorescence wavelength lambda _1em and the second organic organics maximum excitation wavelength lambda _2EX is characterized in that a relation of the following equation (Equation (1)), one of the claims 1 to 14 The wavelength conversion type sealing material layer of crab.
[Formula (1)]
_{λ 1em -80 ≦ λ 2ex ≦ λ} 1em +100 (nm)   The wavelength conversion according to claim 1, wherein the first organic substance includes at least one selected from the group consisting of a perylene derivative, a benzoxazole derivative, a benzothiadiazole derivative, a benzotriazole derivative, and a fluorene derivative. Mold sealing material layer.   The wavelength conversion according to any one of claims 1 to 16, wherein the second organic substance includes at least one selected from the group consisting of a perylene derivative, a benzoxazole derivative, a benzothiadiazole derivative, a benzotriazole derivative, and a fluorene derivative. Mold sealing material layer.   The wavelength conversion type sealing material layer in any one of Claims 1-17 used for a solar cell use.   The solar cell module containing the wavelength conversion type sealing material layer in any one of Claims 1-18, and a photovoltaic cell. The solar cell is a crystalline silicon solar cell, an amorphous silicon solar cell, a microcrystalline silicon solar cell, a thin film silicon solar cell, a heterojunction solar cell, a multijunction solar cell, a cadmium sulfide / cadmium telluride solar cell, or a CIS system. The solar cell module according to claim 19, which is a thin film solar cell, a CIGS thin film solar cell, a CZTS thin film solar cell, a III-V group solar cell, a dye-sensitized solar cell, or an organic semiconductor solar cell.

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